Irena Kratochvílová

Room temperature negative differential resistance in molecular nanowires

Electric-field assisted assembly has been used to place rod-shaped metal nanowires containing 4-{[2-nitro-4-(phenylethynyl)phenyl]ethynyl}benzenethiol molecules onto lithographically defined metal pads. In these systems the current–voltage characteristics exhibited negative differential resistance at room temperature with on–off peak-to-valley ratios of 1.80 to 2.21.

Growth and characterization of nanodiamond layers prepared using the plasma-enhanced linear antennas microwave CVD system

Industrial applications of plasma-enhanced chemical vapour deposition (CVD) diamond grown on large area substrates, 3D shapes, at low substrate temperatures and on standard engineering substrate materials require novel plasma concepts. Based on the pioneering work of the group at AIST in Japan, the high-density coaxial delivery type of plasmas has been explored (Tsugawa et al 2006 New Diamond Front. Carbon Technol. 16 337–46). However, an important challenge is to obtain commercially interesting growth rates at very low substrate temperatures. In this work we introduce the concept of novel linear antenna sources, designed at Leybold Optics Dresden, using high-frequency pulsed MW discharge with a high plasma density. This type of pulse discharges leads to the preparation of nanocrystalline diamond (NCD) thin films, compared with ultra-NCD thin films prepared in (Tsugawa et al 2006 New Diamond Front. Carbon Technol. 16 337–46). We present optical emission spectroscopy data for the CH4–CO2–H2 gas chemistry and we discuss the basic properties of the NCD films grown.

Metallochelating liposomes with associated lipophilised norAbuMDP as biocompatible platform for construction of vaccines with recombinant His-tagged antigens: Preparation, structural study and immune response towards rHsp90

Hsp90-CA is present in cell wall of Candida pseudohyphae or hyphae-typical pathogenic morphotype for both systemic and mucosal Candida infections. Heat shock protein from Candida albicans (hsp90-CA) is an important target for protective antibodies during disseminated candidiasis of experimental mice and human. His-tagged protein rHsp90 was prepared and used as the antigen for preparation of experimental recombinant liposomal vaccine. Nickel-chelating liposomes (the size around 100nm, PDI≤0.1) were prepared from the mixture of egg phosphatidyl choline and nickel-chelating lipid DOGS-NTA-Ni (molar ratio 95:5%) by hydration of lipid film and extrusion methods. New non-pyrogenic hydrophobised derivative of MDP (C18-O-6-norAbuMDP) was incorporated into liposomes as adjuvans. rHsp90 was attached onto the surface of metallochelating liposomes by metallochelating bond and the structure of these proteoliposomes was studied by dynamic light scattering, AF microscopy, TEM and GPC. The liposomes with surface-exposed C18-O-6-norAbuMDP were well recognised and phagocyted by human dendritic cells in vitro. In vivo the immune response towards this experimental vaccine applied in mice (i.d.) demonstrated both TH1 and TH2 response comparable to FCA, but without any side effects. Metallochelating liposomes with lipophilic derivatives of muramyl dipeptide represent a new biocompatible platform for construction of experimental recombinant vaccines and drug-targeting systems.

Theoretical and Experimental Study of Charge Transfer through DNA: Impact of Mercury Mediated T-Hg-T Base Pair

DNA-Hg complexes may play an important role in sensing DNA defects or in detecting the presence of Hg in the environment. A fundamental way of characterizing DNA-Hg complexes is to study the way the electric charge is transferred through the molecular chain. The main goal of this contribution was to investigate the impact of a mercury metal cation that links two thymine bases in a DNA T-T mismatched base pair (T-Hg-T) on charge transfer through the DNA molecule. We compared the charge transfer efficiencies in standard DNA, DNA with mismatched T-T base pairs, and DNA with a T-Hg(II)-T base pair. For this purpose, we measured the temperature dependence of steady-state fluorescence and UV-vis of the DNA molecules. The experimental results were confronted with the results obtained employing theoretical DFT methods. Generally, the efficiency of charge transfer was driven by mercury changing the spatial overlap of bases.

Conductivity of natural and modified DNA measured by scanning tunneling microscopy. The effect of sequence, charge and stacking

The conductivity of DNA covalently bonded to a gold surface was studied by means of the STM technique. Various single- and double-stranded 32-nucleotide-long DNA sequences were measured under ambient conditions so as to provide a better understanding of the complex process of charge-carrier transport in natural as well as chemically modified DNA molecules. The investigations focused on the role of several features of DNA structure, namely the role of the negative charge at the backbone phosphate group and the related complex effects of counterions, and of the stacking interactions between the bases in Watson-Crick and other types of base pairs. The measurements have indicated that the best conductor is DNA in its biologically most relevant double-stranded form with Watson-Crick base pairs and charged phosphates equilibrated with counterions and water. All the studied modifications, including DNA with non-Watson-Crick base pairs, the abasic form, and especially the form with phosphate charges eliminated by chemical modifications, lower the conductivity of natural DNA.

Charge Transport in DNA Oligonucleotides with Various Base-Pairing Patterns

We combined various experimental (scanning tunneling microscopy and Raman spectroscopy) and theoretical (density functional theory and molecular dynamics) approaches to study the relationships between the base-pairing patterns and the charge transfer properties in DNA 32-mer duplexes that may be relevant for identification and repair of defects in base pairing of the genetic DNA and for DNA use in nanotechnologies. Studied were two fully Watson-Crick (W-C)-paired duplexes, one mismatched (containing three non-W-C pairs), and three with base pairs chemically removed. The results show that the charge transport varies strongly between these duplexes. The conductivity of the mismatched duplex is considerably lower than that of the W-C-paired one despite the fact that their structural integrities and thermal stabilities are comparable. Structurally and thermally much less stable abasic duplexes have still lower conductivity but not markedly different from the mismatched duplex. All duplexes are likely to conduct by the hole mechanism, and water orbitals increase the charge transport probability.

Immobilization of histidine-tagged proteins on monodisperse metallochelation liposomes: Preparation and study of their structure

Liposomes represent a biocompatible platform for the construction of self-assembling proteoliposomes using nickel or zinc metallochelation. Potential applications of such structures consist in the development of new biocompatible vaccination nanoparticles and drug delivery nanoparticle systems. Here, we describe the design and construction of a flow-through ultrafiltration cell suitable for the preparation of monodisperse liposomes enabled for metallochelation and, hence, the formation of proteoliposomes. The linkage of the cell with a fast protein liquid chromatography system facilitates automation of the procedure, which fits the criteria for upscaling. Proof-of-concept experiments are performed using a mixture of egg phosphatidyl choline and nickel-chelating lipid DOGS-NTA-Ni (1,2-dioleoyl-sn-glycero-3-{[N(5-amino-1-carboxypentyl)iminodiacetic acid]succinyl}(nickel salt)) to formulate proteoliposomes with proteins attached by metallochelation, including histidine (His)-tagged recombinant green fluorescent protein and rgp120 (derived from HIV-1 Env). These model proteoliposomes are characterized by gel permeation chromatography and by dynamic light scattering. Transmission electron microscopy and immunogold staining are used to characterize surface-bound proteins, revealing the tendency of rgp120 to form microdomains on liposome surfaces. These microdomains possess a two-dimensional crystal-like structure that is seen more precisely by atomic force microscopy.

New organic FET-like photoactive device, experiments and DFT modeling.

Abstract.We present the possible construction of an organic FET-like photoactive device in which source-drain current through a phthalocyanine ( H2Pc film is affected by a photo-induced dipolar field in a photoactive “gate” electrode. The influence of the dipolar electric field on charge transfer between H2Pc molecules is modeled by DFT quantum-chemical calculations on H2Pc dimers and tetramers.

CURRENT-VOLTAGE CHARACTERIZATION OF ALKANETHIOL SELF-ASSEMBLED MONOLAYERS IN METAL NANOWIRES

An electric-field assisted assembly has been used to place rod-shaped, metal-organic, molecule-metal nanowires onto lithographically defined metal pads allowing the electrical characterization of metal-molecule self-assembled monolayer-metal containing nanowires. Our results show that the parameters of metal-molecule metal junctions are close to previously published data, so we have constructed systems containing insulating monolayers with reasonable properties.

Scanning tunneling spectrosopy study of DNA conductivity

We used STM to study the conductivity of 32 nucleotide long DNA molecules chemically attached to a gold surface. Two oligonucleotides containing all four base types namely G, A, C, T, one single stranded and one double helical, all showed conductance data significantly higher than DNA containing only T and A that were either single stranded d(T32) or double helical d(T32).d(A32) in confirmation. Within each sequence group, the conductivity of the double helical form was always higher than that of the single strand. We discuss the impact of structure, particular base stacking and affinity to the phase transition.